Monoazo compounds containing a pyrazolone

ABSTRACT

A COLORED AZO COUPLER OF THE FORMULA   1-(R-NH-CO-),3-(PHENYL-NH-),4-((3-Y,4-HO,5-X-PHENYL)-   N=N-)PYRAZOLIN-5-ONE   WHEREIN Y IS HYDROGEN, HALOGEN OR CARBOXYL, X IS HALOGEN OR CARBOXYL, AND R IS AN ARYL RADIDCAL HAVING AT LEAST ONE WATER-SOLUBILIZING GROUP AND AT LEAST ONE GROUP IMPARTING NON-DIFFUSIVITLY TO THE COUPLER.

Int. Cl. (10% 29/38 US. O]. 260-163 8 Claims ABSTRACT OF THE DISCLOSURE A colored azo coupler of the formula CO-NH-R wherein Y is hydrogen, halogen or carboxyl, X is halogen or carboxyl, and R is an aryl radical having at least one water-solubilizing group and at least one group imparting non-diffusivity to the coupler.

This application is a division of application Ser. No. 547,189, filed May 3, 1966, now US. Pat. 3,476,564.

This invention relates to novel compounds and their use as colored couplers in color photography.

It is known that colored images produced in multilayer film constructions by chromogenic development often results in unsatisfactory color rendition due to secondary absorptions by the image-forming indophenol or azomethine dyes. Correction is normally accomplished by the use of colored masks which are produced during the chromogenic development, such masks being provided by using colored coupler materials. For example, whereas colorless couplers of the alpha-naphthol type provide a blue image on a colorless background, colored couplers of the 4-phenylazo-1-naphthol type provide blue images on an orange or magenta background. Likewise, whereas colorless couplers of the pyrazolone type produce magenta images on a colorless background, colored couplers of the 4-phenylazo-pyrazolone type produce magenta images on a yellow background. Further information on the mechanism of such reactions and on masking technology can be obtained from Vittum, Sawdey, Herdle and 'Scholl, EI.A.C.S. 72, p. 1533 (1950); Vittum and Brown, I.A.C.S. 68, p. 2235 (1946); Evans, Hanson, Jr., and Brewer, Principles of Color Photography, p. 565 and fol.

One of the problems encountered with the use of colored couplers is a decreased reactivity in the coupling reaction as compared with corresponding colorless cou- 3,657,216 Patented Apr. 18, 1972 pler. As a result, sensitivity is decrased, often to the point of rendering the colored coupler essentially useless. The low reactivity of such colored couplers appears to be an intrinsic characteristic of the colored azo coupler com- 5 pounds, perhaps due to either the structure of the original colorless coupler or the structure of the diazotized molecule used to obtain the azo dye or to the entire structure of the moieties joined by the azo radical. This lower reactivity is observed most frequently in colored couplers 10 of the 4-arylazo-pyrazolone class which correspond to In US. Pat. No. 2,983,608 colored pyrazolone coupler compounds are described which, because of certain substitution on the pyrazolone ring, are stated to be sufficiently reactive to provide compensation for unwanted blue absorption of the magenta dye produced upon color development. However, considerable improvement in reactivity of colored couplers without lowering the molar extinction coefficient has been desired.

It is therefore an object of this invention to provide new colored couplers having relatively high coupling reactivity. Other objects and advantages will be apparent from the following description.

In accordance with this invention it has been found at colored couplers having the aforementioned advantages are represented by the structural formula wherein Y is hydrogen, halogen (e.g. chlorine, bromine), or carboxyl, X is halogen or carboxyl, and R is hydrogen, alkyl (e.g. 0 -0 alkyl) or aryl (including substituted aryl, e.g. substituted phenyl). Preferably R is an aryl radical having a water solubilizing group (e.g. carboxylic acid or salt thereof, sulfonic acid or salt thereof, sulfamidic group, etc.) and a group imparting non-diffusibility and substantivity (e.g. long chain or C -C alkyl carboxamido groups, etc.). Such couplers are particularly characterized by their high degree of reactivity in the chromogenic development reaction. Of particular value are those couplers in which R comprises p-phenylsulfonamidophenyl.

The high molar extinction coelficient of this class of yellow dyes can be illustrated by comparing one of the preferred dyestuffs of this invention with well known colored couplers. The colored coupler COOH NHC O CnHu exhibits a molar extinction coeflicient in butyl acetate of 2.38X10 whereas the coupler '4 of the resultingmagenta. dye are, essentially the same as described in Italian Pat. No. 632,532, since the same dye and coupler have a corresponding molar extinction coefficient in butyl acetate of 1.89 and 231x10 respectively. The

2,983,608, including their molar extinction coefficients.

Comparison of these molar extinction coeificients indicates that the colored couplers of the present invention also display a high value for the molar extinction coefiicient and accordingly can be used in relatively small quantities in the photographic emulsion. Moreover, it is alternatively possible to use the colored couplers of this invention in thinner layers, thereby permitting greater definition and improved resolution of the photographic material.

The colored couplers of this invention are particularly suitable for use in negative-type color photographic materials capable of yielding, by printing on paper or color positive film, faithful reproduction of the original image with good saturation and improved sharpness. These color couplers may be employed as the only coupler material in a photosensitive layer, or they may be used in admixture with colorless couplers to further control the masking effect.

CsHn (tertiary) H1! (tertiary) is formed. Superimposed on the magenta colored negative image is a yellow colored positive image of the original subject, representing the masking image which, upon printing from the negative using suitable filters, compensates for the undesirable light absorption of the magenta dye.

The following examples illustrate the preparation of the colored couplers of this invention, it being understood that they are presented for. purposes of illustration and not of limitation.

EXAMPLE 1 77.5 grams of l-p-(3'-carboxy-5'-stearoyl aminophenylsulfamyl) phenylcarbamyl-3-anilino-5 pyrazolone were dissolved in 900 ml. of water and 25 ml. of 36 Baum caustic soda. This solution was neutralized using thiazole yellow as indicator and 40 grams of sodium carbonate. To this solution, stirred and cooled to 0 C., was added over a period of one-half hour an aqueous solution of the diaznium salt from 14.3 grams of 2-chloro-4-aminophenol. Stirring was continued until the reaction was complete, and the mixture was acidified with hydrochloric acid, using Congo Red as indicator. The product was then recovered by filtration, was washed to neutrality with cold water, and was then crystallized from acetic acid. The colored product had the formula:

N (caleulated=12.05% N (found) 11.39

absorptl By exposing to a light image a sample of a silver halide photographic material comprising an emulsion layer which is sensitized to green light and which contains a color coupler of this invention, a magenta colored negative image of the original subject can be produced by conventional chromogenic development with a N,N-di- 7 on peak hi dlmothyliormamide=4l0 mlllimierons N (calculated) 12.05% N (found)=l1.39% Absorption peak in dimethylformamide=4l0 millimicrons EXAMPLE 2 Following the procedure of Example 1, with the subethyl-p-phenylenediamine developer. The characteristics stitution of a solution of the diazonium salt obtained from 19 grams of 2-brom o-4-aminophenol for the diazonium and additional uses therefore will be apparent to those salt of 2-ch1oro-4-aminophenol, the followmg colored couskilled in the art without departing from the scope or pler was obtained: spirit of this diclosure. t-

| CO N COOH N (calculated)=l1.51% What is claimed is: N (found)=1l.39% 1. A colored azo coupler of the formula absorption peak in dimethylformamide=410 millimicrons EXAMPLE 3 x Following the procedure of Example 1, with the sub- H0 N N CH--C NH stitution of a solution of the diazonium salt obtained 0 from 22.4 grams of 2,6 dichloro 4 aminophenol for the diazonium salt of 2chloro-4-aminophenol, the follow '7 NH R ing colored coupler was obtained:

N (calculated)=l1.66%

absorption peak in d1methylformam1de=4l0 millimicrons wherein Y is hydrogen, halogen or carboxyl, X is ha1o EXAMPLE 4 gen or carboxyl, and R is a p-phenylsulfonamidophenyl radical having bonded to the terminal phenyl ring thereof a water-solubilizing group and a group imparting nondiifusivity to the coupler.

DEE-C O-GnHs COQH Following the procedure of Example 1, with the substit-ution of a solution of the diazonium salt obtained from 26.6 grams of 2,6 dibromo 4 amino'phenol for the diazonium salt of 2 chloro 4 aminophenol, the following colored coupler was obtained:

00 N R Br NH-CO-C H f I C Hs own-Q ('JOOH N (calculated)=l0.56% 2. A colored azo coupler of the formula N (f0und)=10.31% 2! absorption peak in dimethylformamide=4l0 millimicrons no N N c M EXAMPLE 5 i O a if Following the procedure of Example 1, with the substitution of a solution of the diazonium salt obtained from co m; R 15 .3 grams of S-aminosalicylic acid for the diazonium salt wherein Y is hydrogen, halogen or carboxyl, X is halogen of 2 chloro 4 aminophenol, the following colored or carboxyl,-and R is a p-phenylsulfonamidophenyl,radicoupler was obtained: cal having bondcdto the terminal phenyl ring thereof a JOOH N (alcu1ated)=1195 water-solubilizing group which is a carboxylic acid or N (found)==11.0 0% I i I sgltthereqf, asulfonic acid or salt thereof or a sulfarnidic absolpuon peak m methanl=430 Imnlmlcmns group; and an alkylcarboxamido group imparting non- Various other embodiments of the present invention 7 diffusibility and substantivity to the coupler.

3. A colored azo coupler suitable for use in color photography and having the formula I wherein Y is hydrogen, halogen or carboxyl, X is halogen or carboxyl, and Alk is a C -C alkyl group.

4. The colored azo coupler of claim 3 having the formula NHCOCHHH 5. The colored azo coupler of claim 3 having the formula B;- NHCOCnHu N l ONH-Q- s OzNHQ COOH 6. The colored azo coupler of claim 3 having the formula 7. The colored azo coupler of claim 3 having the formula Br HON=NCH-fi-NH- 0:4: N Br NHCOCuHgs I| I l c oNH-s omit-Q c0011 8. The colored azo coupler of claim 3 having the formula H0 N=N-OH("3NH- 0:6 N COOH 000B 1}! l conn--s OQNHQ NHCOCrIHss References Cited UNITED STATES PATENTS 2,983,608 5/1961 Beavers 260-163 X JOSEPH REBOLD', Primary Examiner D. M. PAPUGA, Assistant Examiner US. Cl. X.R. 260-310 A 

